The title compound, C5H3N3OS, is almost planar (r.m.s. deviation for the ten non-H atoms = 0.018 Å) and forms an extended layer structure in the (100) plane, held together via hydrogen-bonding interactions between adjacent molecules. Of particular note is the occurrence of RC-HN-=N+=NR interactions between an aromatic C-H group and an azide moiety which, in conjunction with a complementary C-HO=C interaction, forms a nine-membered ring.

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